Shape memory materials (SMPs) feature an ability to transform shape from a temporary shape to a permanent shape when triggered by an environmental stimulus, such as heat, light, or vapor. These phenomena can be exploited for a wide range of applications. SMPs intrinsically exhibit shape memory effects derived from their highly coiled constituent chains that are collectively extensible via mechanical work and this energy may be stored indefinitely, known as “shape fixing,” by cooling below glass transition temperature (Tg) or melting temperature (Tm). The polymeric samples can later perform mechanical work and return to a stress-free state when heated above the critical temperature, mobilizing the frozen chains to regain the entropy of their coiled state. Thermally stimulated SMPs have the advantages of: (i) large recoverable deformations in excess of several hundred percent strain; (ii) facile tuning of transition temperatures through variation of the polymer chemistry; and (iii) processing ease at low cost.